CN110257640A - A kind of method that wiring board burns cigarette ash comprehensive reutilization - Google Patents
A kind of method that wiring board burns cigarette ash comprehensive reutilization Download PDFInfo
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- CN110257640A CN110257640A CN201910678545.0A CN201910678545A CN110257640A CN 110257640 A CN110257640 A CN 110257640A CN 201910678545 A CN201910678545 A CN 201910678545A CN 110257640 A CN110257640 A CN 110257640A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of methods that wiring board burns cigarette ash comprehensive reutilization, it is absorbed including concentrated sulfuric acid mixing, heating destructive distillation, cooling absorption, chlorine displacement, lime white, water dissolution, zinc oxide neutralization, zinc dust precipitation, ammonium acetate dissolving step, the present invention is using the removing of sulfuric acid low temperature retorting technique and recovery train plate burns bromine, chlorine in cigarette ash, then copper, lead, zinc, tin are recycled respectively using targetedly technical solution one by one, and is able to achieve the efficiently concentrating of the noble metals such as gold, silver and palladium.The present invention has many advantages, such as that comprehensive utilization ratio is high, the high and low poison of added value is harmless, and the present invention is wider to the adaptability of raw material, is not related to high temperature, high-alkali operation, easy to implement and manipulation, economic feasibility is higher, has a good application prospect.
Description
Technical field
The present invention relates to a kind of methods that wiring board burns cigarette ash comprehensive reutilization, belong to Industrial Solid Waste comprehensive resource
Utilize technical field.
Background technique
Wiring board is the supporter for being most widely used electronic component, is interconnected heavy between undertaking electronic component
Want carrier.With the continuous development of electronic manufacturing technology, large quantities of old systems is discarded at electric appliance, and then is produced and largely urgently located
The old circuit board of reason.Containing valuable metals such as copper, lead, zinc, tin, gold, silver and palladiums in discarded wiring board, there is synthetical recovery
Value.The recovery process of waste printed circuit board valuable metal mainly includes mechanical sorting, heat treatment, chemical treatment, microbiological treatment
Deng, heat treating process is the wiring board treatment process being most widely used at present, burn rule be most important heat treatment method.Line
Road plate can be generated during burning it is a large amount of burn cigarette ash, be enriched in this part cigarette ash a large amount of copper, lead, zinc, tin, gold,
The metals such as silver and palladium, and content is much higher than common mineral resources, has high comprehensive utilization value.
According to statistics, China handles the amount of waste printed circuit board at million tons or more every year, and correlation burns the yield of cigarette ash about 20,000
Ton or so.Due to, containing a large amount of brominated, chlorine resin type organics, burned in wiring board the chlorine in cigarette ash, bromine content generally compared with
It is high.The presence of these chlorine, bromine can bring adverse effect to the recycling of valuable metal in cigarette ash, and existing recovery process is difficult to realize burn
Burn the efficient synthetical recovery of a variety of valuable metals in cigarette ash.To realize the non-ferrous metals such as copper, lead, zinc, tin, gold, silver and palladium and
The efficient synthetical recovery of noble metal, it is necessary to cigarette ash be burned to wiring board and pre-processed using suitable bromine, chlorine removing process.
Summary of the invention
The present invention burns cigarette ash for comprehensive reutilization wiring board, proposes a kind of wiring board burning cigarette ash synthetical recovery
The method utilized, the present invention is using the removing of sulfuric acid low temperature retorting technique and recovery train plate burns bromine, chlorine in cigarette ash, then adopts
Copper, lead, zinc, tin are recycled respectively one by one with targetedly technical solution, and are able to achieve the height of the noble metals such as gold, silver and palladium
Effect enrichment.The present invention has many advantages, such as that comprehensive utilization ratio is high, the high and low poison of added value is harmless.
To reach above-mentioned technical goal, the technical solution adopted by the present invention is that: a kind of wiring board burning cigarette ash comprehensive utilization
Method, the specific steps are as follows:
(1) concentrated sulfuric acid mixes: wiring board being burned cigarette ash and is uniformly mixed with the concentrated sulfuric acid, wherein wiring board burns cigarette ash and the concentrated sulfuric acid
Mass ratio be 1:0.8 ~ 1:1.2, obtain grey acid blend；
(2) it heats destructive distillation: heating destructive distillation being carried out to the grey acid blend that step (1) obtains, the gas generated in retort process claims
For carbonization gas, the remaining product of destructive distillation are destructive distillation slag；
(3) cooling to absorb: gas cooling being carried out to the carbonization gas of step (2) and shower water cyclic absorption, gained acid solution are
For bromine, chloric acid liquid, the residual gas after shower water cyclic absorption is SO2Exhaust gas；
(4) chlorine is replaced: being passed through circulating chlorine gas in the bromine that obtains to step (3), chloric acid liquid and is carried out chlorine displacement reaction, is replaced
Bromine simple substance out, which is in a liquid state, is sunken to bottom, and the aqueous solution on top is hydrochloric acid solution；
(5) lime white absorbs: by the SO of step (3)2Exhaust gas is passed through in lime white, obtains lime white sediment, lime white precipitating
Object is calcium sulfite；
(6) water dissolves: in the destructive distillation slag of step (2) plus water carries out soluble matter dissolution, obtains dissolving solution out and undissolved
Remaining substance, wherein undissolved remaining substance is lead bullion slag based on lead sulfate, the solution for dissolving out be cupric, zinc,
The acidic multimetallic liquid of tin；
(7) zinc oxide neutralizes: the zinc oxide that particulate is added into the acidic multimetallic liquid of step (6) is neutralized, and gained is newborn
Precipitating is the stanniferous precipitating based on tin subsulfate, and the solution after neutralization is that the copper zinc based on copper sulphate, zinc sulfate is molten
Liquid；
(8) zinc dust precipitation: zinc powder is added into the copper zinc solution of step (7) and carries out copper displacement, it is heavy that displaced elemental copper is formed
It forms sediment, the solution that copper displacement is completed is the zinc sulfate crude liquid based on zinc sulfate；
(9) ammonium acetate dissolves: the lead bullion slag of step (6) being dissolved using ammonium acetate solution, obtains final insoluble matter and ammonium lead
Crude liquid, final insoluble matter are the highly enriched noble metal slags of noble metals such as gold, silver, and the main preservation of lead is in ammonium lead crude liquid.
The pyrolysis temperature of heating destructive distillation is 150 ~ 250 DEG C in step (2), and retorting time is 1.5 ~ 2.0h.
Shower water cyclic absorption in step (3) its recycle the pH that terminal is absorbing liquid and reach -0.6 ~ -0.8.
It is 2.5 ~ 3L/ (Lmin), i.e., the gas that 1L bromine per minute, chloric acid liquid are passed through that chlorine in step (4), which is passed through speed,
Amount is 2.5 ~ 3L, and chlorine replaces the reaction time as 30 ~ 45min.
The concentration of lime white is 40 ~ 50% in step (5), and lime white dosage is 5 ~ 7L/m3。
The mass ratio of destructive distillation slag and water is 1:3 ~ 1:5 in step (6).
It is solution ph is 4.5 ~ 5 that addition zinc sulfate in step (7), which neutralize the terminal of its neutralization,.
The concentration of ammonium acetate solution is 10 ~ 15% in step (9), relatively crude lead skim, and the dosage of ammonium acetate solution is 7 ~ 8L/
kg。
The principle of the present invention is: in the environment of highly acid, bromine, chlorine can be with H+In conjunction with generation HBr and HCl, HBr and HCl
Belong to volatile substance, H2SO4(sulfuric acid) then belongs to volatile-resistant substance, in 150 ~ 250 DEG C of pyrolysis temperatures that the present invention is limited
Under, HBr and HCl can be relatively stable and efficiently evaporate, and generate SO less as far as possible2Equal exhaust gas, the HBr volatilized and
HCl efficiently can be only absorbed by the water and collect, to realize the removing of bromine in cigarette ash, chlorine.
The beneficial effects of the present invention are:
(1) method that wiring board of the present invention burns cigarette ash comprehensive utilization, for the first time in low temperature distillation technology removing cigarette ash bromine,
Chlorine can obtain the stand-alone product of bromine, chlorine, tin, copper, zinc and lead, and can also obtain with the use of targetedly recovery process respectively
Highly enriched noble metal slag, the final efficient utilization realized wiring board and burn cigarette ash.
(2) process flow of the invention is reasonable, wider to the adaptability of raw material, is not related to high temperature, high-alkali operation, is easy to real
It applies and manipulates, economic feasibility is high, has good industrial prospect.
(3) the method for the present invention not only fully utilizes wiring board burning cigarette ash but also method is environmentally protective, less toxic harmless, right
Environmental beneficial, the high-efficiency comprehensive utilization for burning cigarette ash for wiring board provide technical support.
(4) economic feasibility of the present invention is higher, has a good application prospect.
Detailed description of the invention
Fig. 1 is the flow chart for the method that wiring board of the present invention burns cigarette ash comprehensive reutilization.
Specific embodiment
With reference to the accompanying drawings and examples, the invention will be further described.
Embodiment 1: the cigarette ash sample of the present embodiment come from city, Langfang in Hebei Province environmental protection company, bromine, chlorine, copper, lead, zinc,
The content of tin is respectively 28.4%, 12.1%, 5.4%, 4.6%, 6.4%, 8.5%, the content of noble metal gold, silver be respectively 16g/t and
153g/t, as shown in Figure 1, being recycled in accordance with the following steps:
(1) concentrated sulfuric acid mixes: wiring board being burned cigarette ash (rear abbreviation cigarette ash) and is uniformly mixed with the concentrated sulfuric acid, wherein cigarette ash and dense sulphur
The mass ratio of acid is 1:1.2, obtains grey acid blend after mixing；
(2) it heats destructive distillation: heating destructive distillation being carried out to the grey acid blend that step (1) obtains, pyrolysis temperature is 250 DEG C, destructive distillation
Time is 2.0 hours, and the gas generated in retort process is carbonization gas, and the remaining product of destructive distillation are destructive distillation slag；
(3) cooling to absorb: gas cooling being carried out to step (2) carbonization gas and shower water cyclic absorption, the circulation terminal of absorption are
The pH value of absorbing liquid reaches -0.6, and gained acid solution is bromine, chloric acid liquid, and the residual gas after absorption is SO2Exhaust gas；
(4) chlorine is replaced: circulating chlorine gas is passed through in the bromine that obtains to step (3), chloric acid liquid, relative to chlorine bromine, chloric acid liquid, chlorine
The speed that is passed through of gas is 3L/ (Lmin), and chlorine replaces the reaction time as 45min, and it is heavy that the bromine simple substance being displaced will be in a liquid state
In bottom, the aqueous solution on top is hydrochloric acid solution；
(5) lime white absorbs: by the SO of step (3)2Exhaust gas is passed through in lime white, obtains lime white precipitating, wherein lime white
Concentration is 50%, and lime white dosage is 7L/m3, lime white sediment is calcium sulfite；
(6) water dissolves: water being added in step (2) destructive distillation slag and carries out soluble matter dissolution, obtains dissolving solution out and undissolved
Remaining substance, wherein the mass ratio of destructive distillation slag and water is 1:3, and undissolved remaining substance is lead bullion based on lead sulfate
Slag dissolves the acidic multimetallic liquid that solution out is main cupric, zinc, tin；
(7) zinc oxide neutralizes: the zinc oxide that particulate is added into the acidic multimetallic liquid of step (6) is neutralized, the end of neutralization
It is 4.5 that point, which be the pH of solution, and it is stanniferous precipitating based on tin subsulfate that gained new life, which precipitates, the solution after neutralization be with
Copper zinc solution based on copper sulphate, zinc sulfate；
(8) zinc dust precipitation: zinc powder is added into the copper zinc solution of step (7) and carries out copper displacement, it is heavy that displaced elemental copper is formed
It forms sediment, the solution that copper displacement is completed is the zinc sulfate crude liquid based on zinc sulfate；
(9) ammonium acetate dissolves: the lead bullion slag of step (6) being dissolved using ammonium acetate solution, ammonium sulfate concentration is 15%, phase
To lead bullion slag, the dosage of ammonium acetate solution is 8L/kg, obtains final insoluble matter and ammonium lead crude liquid, final insoluble matter be gold,
The highly enriched noble metal slag of the noble metals such as silver, lead then main preservation in ammonium lead crude liquid.
Finally, in resulting different product, the bromine rate of recovery is 90.31%, and the chlorine rate of recovery is 91.45%, and the tin rate of recovery is
92.16%, copper recovery 93.21%, zinc recovery 96.2%, lead recovery 90.15%, gold, silver can divide in noble metal slag
476g/t and 4518g/t are not enriched to it.
Embodiment 2: the cigarette ash sample of the present embodiment comes from Chongqing City's environmental protection company, bromine, chlorine, copper, lead, zinc, tin
Content is respectively 18.9%, 6.7%, 8.2%, 5.8%, 3.3%, 6.5%, and the content of noble metal gold, silver is respectively 18g/t and 242g/
T is recycled in accordance with the following steps:
(1) concentrated sulfuric acid mixes: wiring board being burned cigarette ash (rear abbreviation cigarette ash) and is uniformly mixed with the concentrated sulfuric acid, wherein cigarette ash and dense sulphur
The mass ratio of acid is 1:0.8, obtains grey acid blend after mixing；
(2) it heats destructive distillation: heating destructive distillation being carried out to the grey acid blend that step (1) obtains, pyrolysis temperature is 150 DEG C, destructive distillation
Time is 1.5 hours, and the gas generated in retort process is carbonization gas, and the remaining product of destructive distillation are destructive distillation slag；
(3) cooling to absorb: gas cooling being carried out to step (2) carbonization gas and shower water cyclic absorption, the circulation terminal of absorption are
The pH value of absorbing liquid reaches -0.8, and gained acid solution is bromine, chloric acid liquid, and the residual gas after absorption is SO2Exhaust gas；
(4) chlorine is replaced: circulating chlorine gas is passed through in the bromine that obtains to step (3), chloric acid liquid, relative to chlorine bromine, chloric acid liquid, chlorine
The speed that is passed through of gas is 2.5L/ (Lmin), and chlorine replaces the reaction time as 30min, and the bromine simple substance being displaced will be in a liquid state
It is sunken to bottom, the aqueous solution on top is hydrochloric acid solution；
(5) lime white absorbs: by the SO of step (3)2Exhaust gas is passed through in lime white, obtains lime white precipitating, wherein lime white
Concentration is 45%, and lime white dosage is 6L/m3, lime white sediment is calcium sulfite；
(6) water dissolves: water being added in step (2) destructive distillation slag and carries out soluble matter dissolution, obtains dissolving solution out and undissolved
Remaining substance, wherein the mass ratio of destructive distillation slag and water is 1:4, and undissolved remaining substance is lead bullion based on lead sulfate
Slag dissolves the acidic multimetallic liquid that solution out is main cupric, zinc, tin；
(7) zinc oxide neutralizes: the zinc oxide that particulate is added into the acidic multimetallic liquid of step (6) is neutralized, the end of neutralization
Point is that the pH of solution is 5, and gained new life precipitating is the stanniferous precipitating based on tin subsulfate, and the solution after neutralization is with sulphur
Copper zinc solution based on sour copper, zinc sulfate；
(8) zinc dust precipitation: zinc powder is added into the copper zinc solution of step (7) and carries out copper displacement, it is heavy that displaced elemental copper is formed
It forms sediment, the solution that copper displacement is completed is the zinc sulfate crude liquid based on zinc sulfate；
(9) ammonium acetate dissolves: the lead bullion slag of step (6) being dissolved using ammonium acetate solution, ammonium sulfate concentration is 10%, phase
To lead bullion slag, the dosage of ammonium acetate solution is 7.5L/kg, and obtaining final insoluble matter and ammonium lead crude liquid, final insoluble matter is
The highly enriched noble metal slag of the noble metals such as gold, silver, lead then main preservation in ammonium lead crude liquid.
Finally, in resulting different product, the bromine rate of recovery is 93.42%, and the chlorine rate of recovery is 92.47%, and the tin rate of recovery is
95.36%, copper recovery 93.17%, zinc recovery 91.73%, lead recovery 93.33%, gold, silver can divide in noble metal slag
517g/t and 6617g/t are not enriched to it.
Embodiment 3: the cigarette ash sample of the present embodiment comes from Chongqing City's environmental protection company, bromine, chlorine, copper, lead, zinc, tin
Content is respectively 23.4%, 8.8%, 5.3%, 4.1%, 5.7%, 10.4%, and the content of noble metal gold, silver is respectively 10g/t and 54g/
T is recycled in accordance with the following steps:
(1) concentrated sulfuric acid mixes: wiring board being burned cigarette ash (rear abbreviation cigarette ash) and is uniformly mixed with the concentrated sulfuric acid, wherein cigarette ash and dense sulphur
The mass ratio of acid is 1:1, obtains grey acid blend after mixing；
(2) it heats destructive distillation: heating destructive distillation being carried out to the grey acid blend that step (1) obtains, pyrolysis temperature is 150 DEG C, destructive distillation
Time is 1.5 hours, and the gas generated in retort process is carbonization gas, and the remaining product of destructive distillation are destructive distillation slag；
(3) cooling to absorb: gas cooling being carried out to step (2) carbonization gas and shower water cyclic absorption, the circulation terminal of absorption are
The pH value of absorbing liquid reaches -0.7, and gained acid solution is bromine, chloric acid liquid, and the residual gas after absorption is SO2Exhaust gas；
(4) chlorine is replaced: circulating chlorine gas is passed through in the bromine that obtains to step (3), chloric acid liquid, relative to chlorine bromine, chloric acid liquid, chlorine
The speed that is passed through of gas is 2.8L/ (Lmin), and chlorine replaces the reaction time as 35min, and the bromine simple substance being displaced will be in a liquid state
It is sunken to bottom, the aqueous solution on top is hydrochloric acid solution；
(5) lime white absorbs: by the SO of step (3)2Exhaust gas is passed through in lime white, obtains lime white precipitating, wherein lime white
Concentration is 45%, and lime white dosage is 6L/m3, lime white sediment is calcium sulfite；
(6) water dissolves: water being added in step (2) destructive distillation slag and carries out soluble matter dissolution, obtains dissolving solution out and undissolved
Remaining substance, wherein the mass ratio of destructive distillation slag and water is 1:3.5, and undissolved remaining substance is lead bullion based on lead sulfate
Slag dissolves the acidic multimetallic liquid that solution out is main cupric, zinc, tin；
(7) zinc oxide neutralizes: the zinc oxide that particulate is added into the acidic multimetallic liquid of step (6) is neutralized, the end of neutralization
Point is that the pH of solution is 5, and gained new life precipitating is the stanniferous precipitating based on tin subsulfate, and the solution after neutralization is with sulphur
Copper zinc solution based on sour copper, zinc sulfate；
(8) zinc dust precipitation: zinc powder is added into the copper zinc solution of step (7) and carries out copper displacement, it is heavy that displaced elemental copper is formed
It forms sediment, the solution that copper displacement is completed is the zinc sulfate crude liquid based on zinc sulfate；
(9) ammonium acetate dissolves: the lead bullion slag of step (6) being dissolved using ammonium acetate solution, ammonium sulfate concentration is 10%, phase
To lead bullion slag, the dosage of ammonium acetate solution is 7L/kg, obtains final insoluble matter and ammonium lead crude liquid, final insoluble matter be gold,
The highly enriched noble metal slag of the noble metals such as silver, lead then main preservation in ammonium lead crude liquid.
Finally, in resulting different product, the bromine rate of recovery is 95.42%, and the chlorine rate of recovery is 90.31%, and the tin rate of recovery is
98.14%, copper recovery 91.41%, zinc recovery 92.03%, lead recovery 91.16%, gold, silver can divide in noble metal slag
131g/t and 721g/t are not enriched to it.
Embodiment 4: the cigarette ash sample of the present embodiment comes from Chongqing City's environmental protection company, bromine, chlorine, copper, lead, zinc, tin
Content is respectively 30.1%, 6.2%, 3.4%, 5.2%, 4.7%, 8.3%, and the content of noble metal gold, silver is respectively 7g/t and 104g/t,
It is recycled in accordance with the following steps:
(1) concentrated sulfuric acid mixes: wiring board being burned cigarette ash (rear abbreviation cigarette ash) and is uniformly mixed with the concentrated sulfuric acid, wherein cigarette ash and dense sulphur
The mass ratio of acid is 1:0.9, obtains grey acid blend after mixing；
(2) it heats destructive distillation: heating destructive distillation being carried out to the grey acid blend that step (1) obtains, pyrolysis temperature is 200 DEG C, destructive distillation
Time is 1.8 hours, and the gas generated in retort process is carbonization gas, and the remaining product of destructive distillation are destructive distillation slag；
(3) cooling to absorb: gas cooling being carried out to step (2) carbonization gas and shower water cyclic absorption, the circulation terminal of absorption are
The pH value of absorbing liquid reaches -0.8, and gained acid solution is bromine, chloric acid liquid, and the residual gas after absorption is SO2Exhaust gas；
(4) chlorine is replaced: circulating chlorine gas is passed through in the bromine that obtains to step (3), chloric acid liquid, relative to chlorine bromine, chloric acid liquid, chlorine
The speed that is passed through of gas is 2.8L/ (Lmin), and chlorine replaces the reaction time as 40min, and the bromine simple substance being displaced will be in a liquid state
It is sunken to bottom, the aqueous solution on top is hydrochloric acid solution；
(5) lime white absorbs: by the SO of step (3)2Exhaust gas is passed through in lime white, obtains lime white precipitating, wherein lime white
Concentration is 40%, and lime white dosage is 5L/m3, lime white sediment is calcium sulfite；
(6) water dissolves: water being added in step (2) destructive distillation slag and carries out soluble matter dissolution, obtains dissolving solution out and undissolved
Remaining substance, wherein the mass ratio of destructive distillation slag and water is 1:5, and undissolved remaining substance is lead bullion based on lead sulfate
Slag dissolves the acidic multimetallic liquid that solution out is main cupric, zinc, tin；
(7) zinc oxide neutralizes: the zinc oxide that particulate is added into the acidic multimetallic liquid of step (6) is neutralized, the end of neutralization
It is 4.8 that point, which be the pH of solution, and it is stanniferous precipitating based on tin subsulfate that gained new life, which precipitates, the solution after neutralization be with
Copper zinc solution based on copper sulphate, zinc sulfate；
(8) zinc dust precipitation: zinc powder is added into the copper zinc solution of step (7) and carries out copper displacement, it is heavy that displaced elemental copper is formed
It forms sediment, the solution that copper displacement is completed is the zinc sulfate crude liquid based on zinc sulfate；
(9) ammonium acetate dissolves: the lead bullion slag of step (6) being dissolved using ammonium acetate solution, ammonium sulfate concentration is 12%, phase
To lead bullion slag, the dosage of ammonium acetate solution is 7L/kg, obtains final insoluble matter and ammonium lead crude liquid, final insoluble matter be gold,
The highly enriched noble metal slag of the noble metals such as silver, lead then main preservation in ammonium lead crude liquid.
Finally, in resulting different product, the bromine rate of recovery is 96.18%, and the chlorine rate of recovery is 92.71%, and the tin rate of recovery is
94.17%, copper recovery 90.58%, zinc recovery 89.88%, lead recovery 91.16%, gold, silver can divide in noble metal slag
92g/t and 1357g/t are not enriched to it.
Above in conjunction with attached drawing, the embodiment of the present invention is explained in detail, protection scope of the present invention and not only
It is confined to above-described embodiment, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that
For those skilled in the art, several improvements and modifications without departing from the principles of the present invention, are answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of method that wiring board burns cigarette ash comprehensive reutilization, which is characterized in that specific step is as follows:
(1) concentrated sulfuric acid mixes: wiring board being burned cigarette ash and is uniformly mixed with the concentrated sulfuric acid, wherein wiring board burns cigarette ash and the concentrated sulfuric acid
Mass ratio be 1:0.8 ~ 1:1.2, obtain grey acid blend；
(2) it heats destructive distillation: heating destructive distillation being carried out to the grey acid blend that step (1) obtains, the gas generated in retort process claims
For carbonization gas, the remaining product of destructive distillation are destructive distillation slag；
(3) cooling to absorb: gas cooling being carried out to the carbonization gas of step (2) and shower water cyclic absorption, gained acid solution are
For bromine, chloric acid liquid, the residual gas after shower water cyclic absorption is SO2Exhaust gas；
(4) chlorine is replaced: being passed through circulating chlorine gas in the bromine that obtains to step (3), chloric acid liquid and is carried out chlorine displacement reaction, is replaced
Bromine simple substance out, which is in a liquid state, is sunken to bottom, and the aqueous solution on top is hydrochloric acid solution；
(5) lime white absorbs: by the SO of step (3)2Exhaust gas is passed through in lime white, obtains lime white sediment, lime white sediment
For calcium sulfite；
(6) water dissolves: in the destructive distillation slag of step (2) plus water carries out soluble matter dissolution, obtains dissolving solution out and undissolved
Remaining substance, wherein undissolved remaining substance is lead bullion slag based on lead sulfate, the solution for dissolving out be cupric, zinc,
The acidic multimetallic liquid of tin；
(7) zinc oxide neutralizes: zinc oxide being added into the acidic multimetallic liquid of step (6) and is neutralized, gained new life precipitating is
Stanniferous precipitating based on tin subsulfate, the solution after neutralization are the copper zinc solutions based on copper sulphate, zinc sulfate；
(8) zinc dust precipitation: zinc powder is added into the copper zinc solution of step (7) and carries out copper displacement, it is heavy that displaced elemental copper is formed
It forms sediment, the solution that copper displacement is completed is the zinc sulfate crude liquid based on zinc sulfate；
(9) ammonium acetate dissolves: the lead bullion slag of step (6) being dissolved using ammonium acetate solution, obtains final insoluble matter and ammonium lead
Crude liquid, final insoluble matter are the highly enriched noble metal slag of noble metal, and the main preservation of lead is in ammonium lead crude liquid.
2. the method that wiring board according to claim 1 burns cigarette ash comprehensive reutilization, it is characterised in that: step (2)
The pyrolysis temperature of middle heating destructive distillation is 150 ~ 250 DEG C, and retorting time is 1.5 ~ 2.0h.
3. the method that wiring board according to claim 1 burns cigarette ash comprehensive reutilization, it is characterised in that:
Shower water cyclic absorption in step (3) its recycle the pH that terminal is absorbing liquid and reach -0.6 ~ -0.8.
4. the method that wiring board according to claim 1 burns cigarette ash comprehensive reutilization, it is characterised in that: step (4)
It is 2.5 ~ 3L/ (Lmin) that middle chlorine, which is passed through speed, and chlorine replaces the reaction time as 30 ~ 45min.
5. the method that wiring board according to claim 1 burns cigarette ash comprehensive reutilization, it is characterised in that:
The concentration of lime white is 40 ~ 50% in step (5), and lime white dosage is 5 ~ 7L/m3。
6. the method that wiring board according to claim 1 burns cigarette ash comprehensive reutilization, it is characterised in that: step (6)
The mass ratio of middle destructive distillation slag and water is 1:3 ~ 1:5.
7. the method that wiring board according to claim 1 burns cigarette ash comprehensive reutilization, it is characterised in that: step (7)
In addition zinc sulfate neutralize the terminal of its neutralization be solution ph is 4.5 ~ 5.
8. the method that wiring board according to claim 1 burns cigarette ash comprehensive reutilization, it is characterised in that: step (9)
The concentration of middle ammonium acetate solution is 10 ~ 15%, relatively crude lead skim, and the dosage of ammonium acetate solution is 7 ~ 8L/kg.
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| CN111983137A (en) * | 2020-08-13 | 2020-11-24 | 楚雄滇中有色金属有限责任公司 | Method for detecting copper in electronic waste |
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